WO2013104993A2 - Procédé de mélange en solution amélioré pour la fabrication de nanocomposites de nylon 6-montmorillonite - Google Patents

Procédé de mélange en solution amélioré pour la fabrication de nanocomposites de nylon 6-montmorillonite Download PDF

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WO2013104993A2
WO2013104993A2 PCT/IB2013/000415 IB2013000415W WO2013104993A2 WO 2013104993 A2 WO2013104993 A2 WO 2013104993A2 IB 2013000415 W IB2013000415 W IB 2013000415W WO 2013104993 A2 WO2013104993 A2 WO 2013104993A2
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clay
nylon
ion
ammonium ion
nanocomposite
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PCT/IB2013/000415
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English (en)
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WO2013104993A3 (fr
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Ahmed M. Abdel GAWAD
Adham R. RAMADAN
Amal M.k. ESAWI
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American University In Cairo
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Priority to US14/371,502 priority Critical patent/US20140350153A1/en
Publication of WO2013104993A2 publication Critical patent/WO2013104993A2/fr
Publication of WO2013104993A3 publication Critical patent/WO2013104993A3/fr
Priority to US15/295,310 priority patent/US10100175B2/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D9/0004—Crystallisation cooling by heat exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D9/005—Selection of auxiliary, e.g. for control of crystallisation nuclei, of crystal growth, of adherence to walls; Arrangements for introduction thereof
    • B01D9/0054—Use of anti-solvent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/50—Mixing liquids with solids
    • B01F23/53—Mixing liquids with solids using driven stirrers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/45—Magnetic mixers; Mixers with magnetically driven stirrers
    • B01F33/452—Magnetic mixers; Mixers with magnetically driven stirrers using independent floating stirring elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • the present disclosure relates generally to nanocomposites and, in particular,
  • Nylon 6-montrnoriUonite clay nanocomposites More specifically, the present disclosure concerns compositions and methods which contain unmodified or organically modified nylon 6-montrnorii Ion ite clays .
  • Nanotechnology is a fast developing field that has attracted attention.
  • One of the important applications of nanotechnology is the manufacturing of nanocomposites.
  • the real interest in nanotechnology is to create revolutionary properties and functions by tailoring materials and designing devices on the nanometer scale.
  • the term “nanocomposites” implies that one of the phases of the composite material (the matrix or the reinforcement phases) is composed of particles or fibers with nano-dimensions.
  • nanocomposites show their vastly improved mechanical properties with a relatively small content of the filler material. This is mainly due to the large surface area of the filler material. Moreover, nanocomposites show other enhancements depending on the filler and the matrix elements. For instance, carbon nanotubes (CNT's) are used in polymer and ceramic matrices to produce electrically conductive nanocomposites. CNT's are also used in combination with metals to make use of the outstanding mechanical properties of the CNT's and the ducti lity of metals like aluminum and copper (Mora et al, 2009).
  • CNT's carbon nanotubes
  • metals to make use of the outstanding mechanical properties of the CNT's and the ducti lity of metals like aluminum and copper (Mora et al, 2009).
  • Clay nanocomposites represent a class of nanocomposites in which the filler element is nanoclay. These materials are known as smectite clays, such as hectorite, montmorillonite (MMT), and synthetic mica. Smectite clays are peculiar in their structure as they are composed of layers. Each layer is built from tetrahedrally coordinated Si atoms fused into an edge shared octahedral plane of Al(OH) 3 or Mg(OH) 2 (Sinha Ray and Okamoto, 2003). The mechanical properties of these individual layers are not yet known. However, some attempts have been made to model the mechanical properties of the silicate layers estimating the Young's modulus along the layer direction to be 50-400 times higher than that of a typical polymer (Gao, 2004). Mechanisms of clay dispersion
  • FIG. 1 shows the structure of the exfoliated and intercalated nanocomposites versus the conventional microcomposite
  • Clay nanocomposites manufactured by Toyota showed an increase in the heat distortion temperature (87°C) and a 45% reduction in the thermal expansion coefficient. This was believed to be due to the reduction in molecular mobility in the polymeric matrix (Fenegge, 2004).
  • Another advantage of clay nanocomposites is their flame retardant properties.
  • clay nanocomposites in contrast to conventional composites, have good optical properties.
  • the composite tends to be opaque due to light scattering at the reinforcing phase whether fibers or particulates.
  • silicate layers do not affect the optical properties of the polymer matrix and, therefore, the resulting composite is transparent. This has been explained using two different interpretations. First, the thickness of the exfoliated clay layers is much less than the wavelength of light thus allowing the light to pass without scattering. Second, in nanocomposites, the size of the reinforcement is in the nanoscale, which allows the formation of composites at the molecular level (Fenegge, 2004).
  • FIG. 2 shows a timing belt cover made from nylon/clay nanocomposite. This was followed by Unikita's attempt to manufacture engine covers for Mitsubishi's engines out of clay/iiyloii6 nanocomposites.
  • eiay/polyolefin nanocomposites were used by General Motors and Basell as a step assistant for GMC Safari and Chevrolet Astro vehicles. Shortly after this, nanocomposites were used for producing the doors of Chevrolet Impalas.
  • clay/polypropylene nanocomposites were used by Noble Polymers in the manufacturing of the seat backs of Hyundai Acura (Fenegge, 2004; and, Okada and Usuki, 2006).
  • the present disclosure relates to nanocomposites based on nylon 6 and montmoriUonite clays and solution blending processes for the fabrication of nanocomposites based on nylon 6 and montmoriUonite clays.
  • This process leads to improved exfoliation and dispersion of montmoriUonite clay layers within the nylon 6 polymer matrix, o vercoming the possible problem of polymer degradation, as well as the limitation of low/no compatibility between the montmoriUonite clays and the nylon 6 polymer for the preparation of the nanocomposite even without the use of highly hydrophobic organic surfactants. Additionally, the process can also be possibly used to produce thin films from nylon 6 clay systems directly.
  • the nanocomposite comprises the reaction product of a polymer such as nylon 6 and a clay such as a montmoriUonite clay.
  • the clay may further comprise an inorganic ion.
  • the inorganic ion can be any inorganic ions known in the art, such as calcium, potassium, sodium, or magnesium.
  • the clay may comprise an organic surfactant.
  • the organic surfactant may have the structure of an ammonium ion modified by one to four carbon-containing R groups (NR4 " ).
  • the R group can be an alky! or aryl group.
  • the organic surfactant does not have a R group that is hydroxyethyl group.
  • Non-limiting examples of organic surfactants lacking hydroxyethyl groups may include dimethyl bis-hydrogenated alky!
  • the organic surfactant may include one or more hydroxyethyl groups, such as methyl bis-2- hydroxyethyl hydrogenated alkyl tallow ammonium ion.
  • nanocomposites may have a high exfoliation as clay platelets are dispersed within the polymer matrix.
  • the degree of exfoliation/dispersion may be about, at least, or at most 10, 20, 30, 40, 50, 100, 150, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1200, 1500, 2000, 2500, 5000, 10,000 platelets/square micron (unr) or any range derivable therein for the clay to exist or disperse in the nanocomposite.
  • the degree of exfoliation may be at least, about, or at most 200, 250, 300, 250, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 1000 clay or any range derivable therein.
  • the degree of exfoliation may be at least, at most, or about
  • the clay comprises an inorganic ion.
  • the degree of exfoliation may be at least, at most, or about 20, 30, 40, 50, 100, 150, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600 platelets/
  • the clay may comprise at least, about, or at most 200, 400, 800, 1000 lateiets/ ⁇ m or any range derivable therein.
  • the nanocomposites can be used for a wide range of applications, such as being comprised into a film, a rubber, an article of manufacture, or a tire.
  • a compatible solvent such as acetic acid
  • a flushing medium such as alcohol
  • the solvent may be acetic acid, formic acid, trichloro acetic acid, phosphoric acid, sulfuric acid, chlorophenol, m-cresol, ethylene carbonate, HMPT (Hexamethylphosphoric Triamide), or mixtures thereof.
  • the volume ratio between solvent and flushing medium is 1 :20, 1 : 1.0, 1 :5, 1 :4, .1 :3, 1 :2, 1 : 1, 2:1 , 3: 1 ; 4: 1 , 5: 1, 10: 1, 20: 1 or any range derivable therein. In a particular aspect, the ratio may be 1 :4.
  • the flushing medium may be any non-aqueous medium or any medium that does not dissolve at most or about 0.1, 0.5, 0.8, I, 5, 10% (or any range derivable therein) solvents.
  • the non-aqueous flushing medium may be alcohol, ester, ether, ketone, chloroform, or a mixtures thereof.
  • the flushing medium may be alcohol such as methanol, ethanol, or propanol; alternatively, the flushing medium may be ester such as methyl formate, ethyl formate, methyl propionate, isobutyl propionate, ethyl propionate, methyl acetate, or ethyl acetate; in other aspects, the flushing medium may be ketone such as acetone, diethyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone. [0024] The flushing medium may be flushed at a flow rate of at least, about, at most
  • the flow rate may be at about 5 to 50 mL/min.
  • this disclosure presents the development of a process and its use to produce 3 types of nylon 6 - moiitmoriilonite nanocomposites (nylon 6/Cloisite Na+, nylon 6/Cloisite 15 A, and nylon6/Cloisite 30B). All of the produced composites were characterized using TEM, XRD, FTIR, MFL and nanoindentation.
  • Results show enhanced exfoliation and dispersion of silicate layers within the polymer matrix for the 3 types of moiitmoriilonite clays used: one with good compatibility between its organic modifier and the nylon 6 polymer (Cioisite 30B); one with low compatibility between its organic modifier and the nylon 6 polymer (Cioisite 15 A); and one with no compatibility due to lack of organic modifier (Cioisite Na+).
  • This novel process surpasses conventional solution blending as well as melt blending with regards to obtained dispersion and exfoliation.
  • FIG. I shows the structure of polymer/layered silicate composites
  • FIG. 2 shows a timing belt cover made from nylon/clay nanocomposite
  • FIG. 3 shows the crystal structure of 2: 1 phyllosilicates
  • FIG. 4 shows the degradation of nyion6 after evaporation of acetic acid
  • FIG. 5 shows the chemical Structure of nylon 6
  • FIG. 6 shows the solution mixing process: (a) stirring of nylon/clay (b) flushing of acetic acid;
  • FIG. 7 shows the compression molding of sample
  • FIG. 8 shows the XRD diffraction patterns for the different samples
  • FIG. 9 shows the XRD diffraction patterns for the different samples
  • FIG. 10 shows the XRD diffraction patterns for the different samples
  • FIG. 11 shows the average nanomdentation modulus values for the different composite samples
  • FIG. 12 shows the average nanomdentation hardness values for the different composite samples
  • FIG. 13 shows the melt flow index of ny!on6/MMT nanocomposites
  • FIG. 14 shows the TEM micrograph for N6-30B prepared by solution compounding
  • FIG. 15 shows the TEM micrograph for N6 ⁇ Na+ prepared by solution compounding
  • FIG. 16 shows the TEM micrograph for N6-15A prepared by solution compounding
  • FIG. 17 shows the FTIR of (a) as-received Cioisite ISA compared to (b) Cioisite 15 A. subjected to the same processing routine used for solution compounding;
  • FIG. 18 shows the FTIR of (a) as-received Cioisite 30B compared to (b)
  • Cioisite 30B subjected to the same processing routine used for solution compounding
  • FIG. 19 shows FTIR of (a) as-received Cioisite Na+ compared to (b) Cioisite
  • FIG. 20 shows the TEM micrograph for N6-30B prepared by static melt annealing
  • FIG. 21 shows the TEM micrograph for N6-Na+ prepared by static melt annealing
  • FIG. 22 shows the TEM micrograph for N6-15A prepared by static melt annealing. DET.AI LED DESCRIPTION OF ⁇ INVENTION
  • Nanocomposites may be inorganic- organic nanocomposites that is a composite in which the inorganic phase is no larger than 1 micron in size, and the organic (polymeric) phase is continuous; that is, nanocomposites are highly dispersed systems of submicron-sized inorganic particles in a polymeric matrix.
  • the inorganic component is a unmodified or modified clay (e.g., modified by comprising organic surfactants) and the organic component is a polymer.
  • the clay used in certain aspects of the invention may include montmorillonite clay (MMT), a member of a group of clay minerals known as "smectite clays" which is a member of a major category of clay minerals known as “2:1 phyllosilicates.”
  • MMT montmorillonite clay
  • smectite clays a member of a major category of clay minerals known as "2:1 phyllosilicates.
  • MMT clays are known to have the highest degree of swelling.
  • MMT clays are widely used commercial ly as a major component of the drilling mud in the oil industry, and a binder for the molding sand. MMT clays are also used for medical applications. See “Montmorillonite.” McGraw-Hill Concise Encyclopedia of Science and Technology. New York: McGraw-Hill, 2006. Credo Reference. Web. 01 January 2012 which is incorporated herein in its entirety by reference.
  • the polymer used in certain aspects of the invention may be Nylon 6.
  • Nylon 6 belongs to a large group of polymers known as "polyamides.” The name denotes the repetition of the amide group (-CO-NH-) in the polymeric chain.
  • a major category of polyamides is synthetic linear aliphatic polyamides, which are commonly referred to as nylons.
  • Nylons are known for their high toughness, tensile strength, impact strength, flexibility as well as their resistance to abrasion.
  • the presence of the amide group in their structure allows the formation of intermolecular hydrogen bonds, which makes them have high degrees of crystallmity and, hence, high melting temperature and tensile strength. See Singh, Jagdamba, and R. C Dubey. Pragati's Organic Polymer Chemistry. Rev, ed. Meerut [India]: Pragati Prakashan, 2009 which is incorporated herein in its entirety by reference.
  • Nylon 6 is one of the most commercially available polyamides. Its monomer is caprolactam which is the cyclic amide of co-aminohexanoic acid (aminocaproic acid).
  • FIG. 5 shows the exemplary chemical structure of nylon 6 monomer having a backbone with six carbon atoms. Nylon 6 may have a general structure as shown below (n as the number of repeating units may be at least 3).
  • the polymers used in the processes disclosed herein may be adapted such that the process uses any polyamide.
  • the polymer or polymer system used herein may be composed of one polymer or a mixture of two or more polymers.
  • the crystal structure of phyllosilicates consists of layers.
  • the building unit of a layer is composed of two silicon atoms per unit making a tetrahedral arrangement that is fused to an-edge shared octahedral aluminum or magnesium hydroxide sheet.
  • Each layer is about 1 nm in thickness with lateral dimensions ranging from 30 nm to microns depending on the structure of the phyllosilicate (Sinha Ray and Okamoto, 2003).
  • Silicate layers are bonded together with van der Waal forces. The gap between these layers is known as the interlamellar, inter! ayer, or gallery gap.
  • Layered silicates have two common characteristics that significantly affect the structure and properties of PLS nanocomposites: (1 ) they can be exfoliated into individual layers; and, (2) it is possible to attach organic and inorganic cations to bond to the surface of silicate layers through ion exchange reaction.
  • the mechanical and thermal properties of composites are generally dependent on the physico-chemical interaction between the matrix and the reinforcing phases. Due to the fact that silicate layers in pristine form are hydro philic and most engineering polymers are organophilic (i.e., hydrophobic), such interaction is not favorable. It is rendered more favorable by incorporating an organic modifier in the clay structure. This is achieved by ion exchange reactions with cations such as primary, secondary, tertiary, and quaternary alkylammonium or alkylphosphonium cations, which also lead to the increase of the distance separating the silicate layers, the intergallery spacing, facilitating the intercalation of the polymer matrix in between these layers.
  • cations such as primary, secondary, tertiary, and quaternary alkylammonium or alkylphosphonium cations
  • solution compounding has been used to prepare PLSN's.
  • the process entails dispersion of clay powders in a dissolved polymer.
  • the silicate layers are dispersed in the polymeric solution, the polymer intercalates them.
  • the polymeric chains are therefore confined due to intercalation. This is expected to decrease the entropy of the whole system.
  • an opposing increase in entropy is gained through desorption of solvent molecules, which compensates the decrease in entropy due to confinement of polymeric chains (Vaia et al., 1997).
  • Static melt annealing presents another approach which has been investigated for the preparation of PLSN's. It is based on the possibility of diffusion of the polymeric chains into clay galleries when the sample is allowed to anneal above its melting temperature.
  • Vaia and Giannelis noted the possibility of intercalation of organically modified silicate layers by Polystyrene.
  • the final structure was found to depend on the time needed for the polymer to diffuse into clay galleries and therefore dependent on the molecular weight of the polymer.
  • the authors suggested that polar interactions between the polymer and the clay layers are essential for the polymer to intercalate the clay galleries.
  • OMLS Organically modified layered silicates
  • Fabrication techniques are commonly used for producing polymer layered silicate nanocomposites (PLSN). In addition to these techniques, there are other processes for fabrication of clay/polymer nanocomposites like solid intercalation, covuicanization, sol-gel method, in-situ formation (Sinha Ray and Okarnoto, 2003), and slurry compounding (Hasegawa et al, 2003). [0067] In-situ polymerization in volves the insertion of monomer between clay layers, and then achieving the dispersion of silicate layers by means of polymerization. This process was first used by Toyota researchers to produce clay/nylon6 nanocomposites. This method showed good exfoliation of the clay in the polymer matrix.
  • melt processing sometimes referred to as melt intercalation, or melt blending is the process of compounding the polymer matrix with the clay during melting (Sinha Ray and Okamoto, 2003), The process, first reported by Vaia et al. (Vaia et al., 1993) is applicable with extrusion and injection molding processes (Sinha Ray and Okamoto, 2003). The technique has been used extensively in the literature to produce exfoliated and intercalated PLS nanocomposites.
  • solutions such as solution blending or in combination with any of the methods available, such as those mentioned above.
  • Soiution- induced intercalation involves the use of solvents to disperse the clay layers in polymeric solutions.
  • the disadvantage of this process can be the high cost associated with some solvents, the availability of compatible solvents, as well as health and safety precautions which can be needed for the process, and which can hinder the commercial use of this process. Exceptions to this are water-soluble polymers (Sinha Ray and Okamoto, 2003).
  • the process can be generally be used with any nanofiller (e.g. smectite clays, carbon nanotubes, fullerenes, ceramic nanoparticies and/or nanorods, metallic nanoparticies and/or nanorods, etc.). It can be used for one type of nanofillers or a combination of two or more types of nanofillers.
  • AH solvents of polyamides can be used. For a particular polymer system, the solvent must dissolve the polymer(s), and must not dissolve, or in any way adversely affect, the nanofiller(s).
  • the process comprises the step of dissolving the polymer in the solvent. This step may be varied by (1) changing the quantities of polymer dissolved in the solvent; (2) changing the temperature at which dissolution is carried out; and/or (3) dissolving more than one polymer in the solvent, or alternatively dissolving each polymer type in its own solvent, then mixing the solutions, [0073] In some embodiments, the process further comprises the step of dispersing the nanofiller in the solvent.
  • This step may be varied by (1) pretreatment of the nanofiller (e.g. chemically for the functionalization of carbon nanotubes, mechanically by ball milling smectite clays to decrease particle size and/or separate the layers); and/or, (2) dispersion of more than one type of nanofiller in one or more solvents.
  • pretreatment of the nanofiller e.g. chemically for the functionalization of carbon nanotubes, mechanically by ball milling smectite clays to decrease particle size and/or separate the layers
  • dispersion of more than one type of nanofiller in one or more solvents e.g. chemically for the functionalization of carbon nanotubes, mechanically by ball milling smectite clays to decrease particle size and/or separate the layers.
  • the process further comprises the step of mixing the dispersed nanofiller and the dissolved polymer and stirring. This step may be varied by changing the time of mixing and stirring in order to ensure good dispersion of the nanofiller within the polymer solution.
  • the process further comprises the step of cooling the mixture.
  • This step may be varied by (1) changing the temperature at which the mixture is cooled; (2) cooling until the mixture solidifies; and/or (3) changing the rate of cooling.
  • the process further comprises the step of flushing the mixture with the washing medium. This step may be varied by (!) changing the ratio of volume of the flushing medium used to the volume of the solvent used to dissolve the polymer; and/or (2) changing the flow rate of the flushing medium over the mixture.
  • the process further comprises the step of evaporation of the flushing medium. This step may be varied by modifying the method of evaporation of the flushing medium. The method of evaporation may be varied depending on the polymer, the solvent, the nanofiller and/or the flushing medium.
  • Acetic and formic acids have been found as solvents for nylon 6 (Polymer handbook, 4th ed., J. Brandrup, E.H. Immergut, and E.A. Grulke, editors ; A. Abe, D.R. Bloch, associate editors, New York: Wiley, 1999).
  • acetic acid was used because it is less harmful, as indicated by material safety data sheets (MSDS) for both acids.
  • MSDS material safety data sheets
  • increments of nylon6 pellets were added to 100 ml of boiling acetic acid (108°C). It was found that saturation occurs after the addition of 1 Og of nylon6.
  • compositions comprising the nanocomposites according to certain aspects of the present invention are described hereinafter, without particularly limiting thereto: nanocomposite automatic timing belt cove, airplane interiors, fuel tanks, components in electrical and electronic parts, under-the- hood automotive structural parts, brakes and tires, or nanocomposite barrier films may be used in food packaging and in other applications,
  • Cloisite 30B is an organically-modified clay obtained by ion exchange of
  • Cloisite 30B has an interlamellar spacing of 18.5 A and a density of 1.98 g/cc,
  • Cloisite 15.A is an organically-modified clay obtained by ion exchange of
  • Cloisite 1.5 A has an interlamellar spacing of 31.5 A and a density of 1 .66 g/cc.
  • Cloisite Na is the natural sodium based MMT. As reported by the supplier,
  • Cloisite Na + has an interlamellar spacing of 11.7 A and a density of 2.86 g/cc.
  • Table 3 Type and Quantity of organic modifiers.
  • FIG. 10 A close investigation of FIG. 8 reveals the existence of a peak for the as-received Cloisite Na + corresponding to a basal spacing of 11.7 A.
  • Cioisite Na to the same processing routine used for solution compounding
  • the peak corresponding to the basal reflection slightly shifted to a lower angle, which corresponds to an increase in the d-spacing between the clay layers, indicating a swelling of the structure as a result of stirring of clay in acetic acid.
  • Cloisite 15A to solution compounding results in the decrease of the basal spacing to 23.56 A
  • the degree of exfoliation was quantified using particle density measurement technique, where the number of clay platelets per unit surface area is determined and used as a measurement of the degree of exfoliation. This was used on the nanocomposite samples (prepared by solution compounding in the Examples), The values are:
  • Cloisite 15 A the values of nanoeomposites made in the Examples range between 400 and 500 platelets/square micron.
  • Closite Na the values of nanoeomposites made in the Examples range between 800 and 1000 platelets/square micron,
  • Nanoindentation testing shows improvement in the mechanical behavior (modulus and hardness) of the nylon 6 sample produced by the solution technique compared to the as-received polymer. This is thought to be due to the solution compounding routine. Dissolution of nylon 6 seemed to result in a structure of fine particles that melt at a faster rate compared to the pel lets used for preparing the as-received reference sample. Since compression molding was carried out at 240°C for a constant time of 5 minutes, solution-compounded samples were melt-armealed for a longer time, which would be expected to result in increasing the molecular weight of the formed samples (Tidick et at., 1984).
  • nylon 6 processed with the same routine used for solution compounding had a higher modulus and hardness than the as- received one. All samples of nylon 6 compounded with the different clays have improved modulus and hardness compared to neat nylon 6 processed using the same processing routine. Samples prepared by static melt annealing (see below) show significant deterioration in their mechanical behavior compared to samples prepared by solution compounding. This is indicative of the fact that the observed improved mechanical properties of the composite samples are a consequence of the solution compounding with no noticeable contribution from static annealing during the compression molding step.
  • Table 4 presents enhancements in nanoindentation modulus and hardness.
  • MFI testing as seen in FIG. 13 shows a significant decrease in MFI for nylon 6 obtained after processing by the solution compounding routine as compared to the as- received polymer, which might be due to the increase in the molecular weight of the polymer as a result of melt annealing for a longer time (Tidiek et al., 1984), as explained before.
  • Ail composite samples exhibit lower MFI values.
  • N6-30B sample was found to have the lowest MFI (highest melt viscosity) possibly due to superior dispersion of and better exfoliation of the silicate layers, evident in the ⁇ images (FIG. 14) and corroborated by the XRD results.
  • N6- 30B composite having a polar organic modifier, thereby more likely to bond with nylon 6, the first factor is expected to prevail leading to full exfoliation and uniform dispersion while in the case of N6-15A composite, having a non-polar organic modifier, the latter factor is expected to prevail leading to lesser exfoliation and a less uniform dispersion of silicate layers.
  • FIGs 17 &18 depict the presence of bands at -2920 cm “1 , ⁇ 2850 cm “1 and at - 1470 cm “1 post solution compounding, which is indicative of the preservation of alkylammonium ions in Cloisite 30B and Cloisite 15 A.
  • the mixture was then compression molded at 240 C for 5 minutes under 65 MPa into cylindrical samples having a diameter of 1 cm and a height of 2 cm.
  • TEM micrographs for statically melt annealed nylon 6-Na+ samples depict clusters of clay particles. No instances of intercalated or exfoliated silicate layers could be observed.
  • nylon 6-15 A samples prepared by static melt annealing, TEM micrographs
  • FIG. 22 reveal non-intercalated clay tactoids.
  • Giannelis E. P. "Polymer Layered Silicate Nanocomposites.” Advanced Materials 8.1 (1996): 29-35. Giannelis, E. P. Polymer-layered silicate nanocomposites: synthesis, properties and applications. Appl, Organomet. ( ' hem. 12, 1998, 675-680.
  • Material Safety Data Sheet Acetic Acid MSDS. Science Lab, 1 1 June 2008. ⁇ http://www.sciencelab.com/msds.php.msdsld 9924100> Material Safety Data Sheet Formic Acid, 85%, F.C.C MSDS. Science Lab, 11 June 2008. ⁇ http://w ⁇ 'w.sciencelab.com, / msds.php.m.sdsld :::: 9924100>.

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Abstract

La présente invention porte d'une façon générale sur des nanocomposites de Nylon 6/argile montmorillonite présentant des propriétés mécaniques renforcées qui ont été préparés principalement par mélangeage en solution. Un problème majeur dans la production des nanocomposites de Nylon 6/argile montmorillonite est associé à l'exfoliation et la dispersion des particules d'argile à l'intérieur de la matrice de polymère. Cette invention porte sur des compositions et des procédés permettant d'obtenir des nanocomposites de Nylon 6/montmorillonite hautement ou totalement exfoliés, non seulement pour des argiles organiquement modifiées présentant une compatibilité connue avec le Nylon 6 (Cloisite 30B), mais également pour des argiles présentant une faible compatibilité ou ne présentant pas de compatibilité avec le Nylon 6 (Cloisite 15A et Na - MMT) grâce au mélangeage en solution.
PCT/IB2013/000415 2012-01-10 2013-01-10 Procédé de mélange en solution amélioré pour la fabrication de nanocomposites de nylon 6-montmorillonite WO2013104993A2 (fr)

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